Hydrocarbon oil composition



United States Patent Ofi ice 3,017,358 HYDROCARBON OIL COMPOSITIONErnest L. Pollitzer, Hinsdale, Ill., assignor, by mes ne assignments, toUniversal Oil Products Company, Des Plaines, 111., a corporation ofDelaware No Drawing. Filed Aug. 8, 1958, Ser. No. 753,894 7 Claims. (Cl.25232.5)

This invention relates to a novel method of preventing heat exchangerdeposits.

In most refining operations economies are effected by utilizing the heatcontained in hot products of the process to partially or completely heatthe charge to the process or other low temperature streams. At the sametime this serves to cool the hot products prior to further separation ortreatment. This transfer of heat normally is accomplished by passing thehot products in indirect heat exchange with the cooler products.However, difiiculty is experienced in the efficient transfer of heat dueto the formation of deposits in the heat exchanger, which depositsinterfere with the satisfactory transfer of heat and, in extreme cases,results in plugging of the heat exchanger. This in turn means that theunit must be completely shut down in order to clean or replace the heatexchanger. It is apparent that this is a serious problem and incursgreat expense in shutting down the. unit, both in the cost of cleaningor replacing the heat exchanger, as well as in the loss of productsto bemarketed. The present invention is directed to a novel method ofpreventing such heat exchanger deposits.

More particularly the present invention is directed to a modification ofcertain additives as will be set forth in detail hereinafter. Theseadditives are effective for use in hydrocarbon oils to improve storageproperties thereof, preventing sediment and sludge formation,discoloration and other undesirable deterioration of the hydrocarbonoil. However, hydrocarbon oils from diflerent sources responddifferently to different additives. Accordingly, the additives referredto above are effective for various purposes in some oils but aresatisfactory for only limited purposes in other oils. For example, someof these additives satisfactorily stabilize the oil againstdeterioration in storage but will not satisfactorily prevent depositformation in heat exchangers. As hereinbefore set forth, the noveladditive of the present invention is particularly effective inpreventing heat exchanger deposits and, at the same time, will serve toimprove the storage stability of hydrocarbon oils.

In one embodiment the present invention relates to a method ofpreventing deposit formation in a heat exchanger through which twofluids at different temperatures are passed, which comprisesincorporating in at least one of said fluids from about 1 to about 1000parts per million by weight of an oil soluble HCl salt of a compoundselected from the group consisting of (1) the condensation product of anepihalohydrin compound With an amine compound, (2) carboxylic acid esterthereof, (3) partial phosphate salt of said condensation product, and(4) partial phosphate salt of said carboxylic acid ester.

In a specific embodiment the present invention relates to a method ofpreventing deposit formation in a heat exchanger through which at leasta portion of a hydrocarbon charge to a process is passed in heatexchange with a portion of hot reactor efiluent products, whichcomprises incorporating in said charge from about 5 to about 100 partsper million by weight of an oil soluble HCl salt of the condensationproduct of epichlorohydrin with tallow amine, said salt having fromabout 1% to about 20% of the amino nitrogen neutralized with HCl.

As hereinbefore set forth, the novel additive of the present inventionis an I-ICl salt of the condensation product of an epihalohydrincompound with an amine 3,017,358 Patented Jan. 16, 1962 compound orderivatives thereof. The condensation product and the derivativesthereof will be described under subheadings to facilitate the expansionof the invention.

CONDENSATION PRODUCT OF EPIHALOI-IYDRIN WITH AMINE 1 Any suitableepihalohydrin compound may be utilized in preparing the condensationproduct thereof with an amine. Epichlorohydrin is preferred. Otherepichlorohydrin compounds include 1,2-epi-4-chlorobutane, 2,3-epi-4-chlorobutane, 1,2-epi-5-chloropentane, 2,3-epi-5- chloropcntane,etc. In general, the chloro derivatives are preferred, although it isunderstood that the corresponding bromo and iodo compounds may beemployed. In some cases epidihalohydrin compounds may be utilized. It isunderstood that the different epihalohydrin compounds are notnecessarily equivalent and that, as hereinbefore set forth,epichlorohydrin is preferred.

Any suitable alkyl amine may be used in preparing the condensationproduct. It is essential that the alkyl amine is a primary or secondaryamine; that is, only one or two of the hydrogen atoms attached to thenitrogen atoms are substituted by alkyl groups, and reference to amineand amine compound in the present specifications and claims is intendedto be limited accordingly. The preferred amine compound is a primaryalkyl amine which, in a specifically preferred embodiment, contains fromabout 12 to about 40 carbon atoms per molecule. Illustrative primaryalkyl amines include dodecyl amine, tridecyl amine, tetradecyl amine,pentadecyl amine, hexadecyl amine, heptadecyl amine, octadecyl amine,nonadecyl amine, eicosyl amine, heneicosyl amine, docosyl amine,tricosyl amine, tetracosyl amine, pentacosyl amine, hexacosyl amine,heptacosyl amine, octacosyl amine, nonacosyl amine, triacontyl amine,hentriacontyl amine, dotriacontyl amine, tritriacontyl amine,tetratriacontyl amine, pentatriacontyl amine, hexatriacontyl amine,heptatriaco-ntyl amine, octatriacontyl amine, nonatriacontyl amine,tetracontyl amine, etc. Conveniently the long chain amines are preparedfrom fatty acids or more particularly from mixtures of fatty acidsformed as products or by-products. Such mixtures are availablecommercially, generally at lower prices and, as another advantage of thepresent invention, the mixtures may be used Without the necessity ofseparating individual amines in pure state.

An example of such a mixture is hydrogenated tallow amine which isavailable under various trade names including Alamine H26D and ArmeenHTD. These products comprising mixtures predominating in alkyl aminescontaining 16 to 18 carbon atoms per alkyl group, although they containa small amount of alkyl groups having 14 carbon atoms, and also meet theother requirements hereinbefore set forth.

Illustrative examples of secondary amines include di- (dodecyl) amine,di-(tridecyl) amine, di-(tetradecyl) amine, di-(pentadecyl) amine,di-(hexadecyl) amine, di(heptadecyl) amine, di-(octadecyl) amine,di-(nonadecyl) amine, di-(eicosyl) amine, etc. In another embodiment,which is not necessarily equivalent, the secondary amine will containone alkyl group having at least 12 carbon atoms and another alkyl grouphaving less than 12 carbon atoms. In most cases both of the alkyl groupshave a straight chain of at least 3 carbon atoms attached to thenitrogen atom. Illustrative examples of such compounds includeN-propyl-dodecyl amine, N-butyl-dodecyl amine, N-amyl-dodecyl amine,N-butyl-tridecyl amine, N-amyl-tridecyl amine, etc. Here again, mixturesof secondary amines are available commercially, usually at a lowerprice, and such mixtures may be used in accordancewith the presentinvention. An example of such a mixture available commercially is Armeen2I-IT which consists primarily of dioctadecyl amine and dihexadecylamine.

Preferred examples of N-alkyl polyamines compriseN-alkyl-l,3-diaminopropanes and still more preferably such compounds inwhich the alkyl group contains at least 12 carbon atoms. Illustrativeexamples include N dodecyl -l,3 diaminopropane, N tridecyl 1,3-diaminopropane, N tetradecyl 1,3 diaminopropane, N pentadecyl 1,3diaminopropane, N hexadecyl- 1,3 diaminopropane, N heptadecyl 1,3diaminopropane, N octadecyl 11,3 diaminopropane, N nonadecyl 1,3diaminopropane, N eicosyl 1,3 diaminopropane,N-heneicosyl-1,3-diaminopropane, N-docosyl- 1,3 diaminopropane, Ntricosyl 1,3 diarninopropane, N-tetracosyl-l,B-diaminopropane,N-pentacosyl- 1,3-diaminopropane, etc. As before, mixtures are availablecommercially, usually at lower prices, of suitable compounds in thisclass and advantageously are used for the purposes of the presentinvention. One such mixture is Duomeen T which isN-tallow-1,3-diaminopropane and predominates in alkyl groups containing16 to 18 carbon atoms each, although the mixture contains a small amountof alkyl groups containing 14 carbon atoms each. Another mixtureavailable commercially is N-coco-1,3-diaminopropane which contains alkylgroups predominating in 12 to 14 carbon atoms each. Still anotherexample is N-soya-l,3-diaminopropane which predominates in alkyl groupscontaining 18 carbon atoms per group, although it contains a smallamount of alkyl groups having 16 carbon atoms.

While the N-alkyl-1,3-diaminopropanes are preferred compounds of thisclass, it is understood that suitable N-alkyl ethylene diamines,N-alkyl-l,3-diaminobutanes, N alkyl 1,4 diaminobutanes, N alkyl 1,3diaminopentanes, N-alkyl-1,4-diaminopentanes, N-alkyl- 1,5diaminopentanes, N alkyl 1,3 diaminohexanes, N-alkyl-1,4-diaminohexanes,N-alkyl-1,5-diaminohexanes, N-alkyll,6-diaminohexanes, etc. may beemployed but not necessarily with equivalent results. Also, it isunderstood that polyamines containing 3 or more nitrogen atoms may beemployed in some cases. In other cases, polyamino alkanes may beemployed as, for example, 1,12-diaminodecane, 1,13-diaminotridecane,etc.

In general the preferred amine compounds are saturated; i.e., do notcontain double bonds in the chain. However, in some cases, unsaturatedcompounds may be employed, although not necessarily with equivalentresults. Such amine compounds may be prepared from unsaturated fattyacids and, therefore, may be available commercially at lower cost.Illustrative examples of such amine compounds include dodecylenic amine,didodecylenic amine, N-dodecylenic ethylene diamine,N-dodecylenic-l,S-diaminopropane, oleic amine, dioleic amine, N-oleicethylene diamine, N-oleicl,3-diaminopropane, linoleic amine, dilinoleicamine, N-linoleic ethylene diamine, N-linoleic-l,3-diaminopropane, etc.It is understood that these amine compounds are included in the presentspecifications and claims by reference to amine or amine compounds.

In another embodiment of the invention, two different amines may bereacted with the epihalohydrin compound. Both of the amines may beselected from those hereinbefore set forth or one of the amines isselected from those hereinbefore set forth and the other amine isselected from ethylene diamine, diethylene triamine, triethylenetetramine, tetraethylene, pentamine, etc., similar propylene andpolypropylene polyamines, butylene and polybutylene polyamines, etc.

In general, 1 or 2 mols of amine compound are reacted with 1 or 2 molsof epihalohydrin compound. It is understood that, in some cases, anexcess of amine or of epihalohydrin may be supplied to the reaction zonein order to insure complete reaction, the excess being removedsubsequently in any suitable manner. When 2 mols of amine are reactedper mol of epihalohydrin compound, the amine may comprise the same ordifferent amine compound.

In a preferred embodiment, the reaction of 1 mol of amine compound with1 mol of epihalohydrin compound proceeds to the formation of polymericreaction product. In this embodiment, the reaction is first effected ata temperature within the range hereinafter set forth, with only aportion of the reactants being present in the reaction mixture. Afterthe initial reaction is completed, the remaining reactants are suppliedto the reaction mixture and the reaction is completed at a highertemperature but within the same range set forth herein. For example, aportion of the amine may be first reacted with the epihalohydrin andthen the remaining portion of the amine is reacted. These polymers maycontain from about 3 to about 20 or more recurring units and preferablyfrom about 5 to about 10 recurring units.

The desired quantity of alkyl amine and epihalohydrin compounds may besupplied to the reaction zone and therein reacted, although generally itis preferred to supply one reactant to the reaction zone and thenintroduce the other reactant step-wise. Thus, usually it is preferred tosupply the amine to the reaction zone and to add the epihalohydrincompound step-wise, with stirring. When it is desired to react twodifferent alkyl amines with the epihalohydrin compound, theepihalohydrin compound is supplied to the reaction zone. One of theamines is added gradually, and the reaction completed, followed by theaddition of the second alkyl amine. Generally, it is preferred toutilize a solvent and, in the preferred embodiment, a solution of theamine in a solvent and a separate solution of the epihalohydrin compoundin a solvent are prepared, and these solutions then are commingled inthe manner hereinbefore set forth. Any suitable solvent may be employed,a particularly suitable solvent comprising an alcohol including ethanol,propanol, butanol, etc., 2-propanol being particularly desirable.

The reaction is effected at any suitable temperature, which generallywill be within the range of from about 20 to about C. and preferably iswithin the range of from about 50 to about 75 C. A higher temperaturerange of from about 30 .to about C. or more, and preferably of fromabout 50 to about 100 C., is specified when the reaction is effected atsuperatmospheric pressure to increase the reaction velocity.Conveniently, this reaction is effected by heating the amine solution atrefluxing conditions, with stirring, gradually adding the epihalohydrincompound thereto, and continuing the heating until the reaction iscompleted.

Either before or after removal of the reaction product from the reactionzone, the product is treated to remove halogen, generally in the form ofan inorganic halide as, for example, the sodium halide. This may beeffected in any suitable manner and generally is accomplished byreacting the product with a strong inorganic base such as sodiumhydroxide, potassium hydroxide, etc., to form the corresponding metalhalide. The reaction to form the metal halide generally is effectedunder the same conditions as hereinbefore set forth. After this reactionis completed, the metal halide is removed in any suitable manner,including filtration, centrifugal separation, etc. It is understood thatthe reaction product also is heated sufficiently to remove alcohol andwater and this may be effected either before or after the treatment toremove the inorganic halide.

In still another embodiment, after the reaction product of an alkylamine and epihalohydrin is prepared, the reaction product may be reactedwith other nitrogen-containing compounds including, for example, alkanolamines, urea, etc., instead of with the same or different alkyl amine ashereinbefore described. Illustrative alkanol amines include ethanolamine, propanol amine, butanol amine, pentanol amine, hexanol amine,etc.

ESTER OF THE CONDENSATION PRODUCT As hereinbefore set forth, anotherembodiment of the present invention comprises an HCl salt of an ester ofthe condensation product of epi'halohydrin compound and amine compound.Any suitable carboxylic acid may be used in forming the ester and in oneembodiment preferably comprises a monobasic carboxylic acid containingat least 6 carbon atoms, more particularly from 6 to about 25 carbonatoms, and thus includes caproic, caprylic, lauric, myristic, palmitic,stearic, arachidic, behenic, lignoceric, cerotic, etc., decylenic,dodecylenic, palrnitoleic, oleic, ricinoleic, petroselinic, vaccinic,linoleic, linolenic, eleostearic, licanic, parinaric, gado leic,arachidonic, cetoleic, erucic, selacholeic, etc. However, in some cases,lower monobasic carboxylic acids may be employed and thus includeformic, acetic, propionic, butyric, valeric, tn'methylacetic, etc.

In another embodiment a polycarboxylic acid is used in forming the esterand preferably comprises a dibasic carboxylic acid containing at least 6and preferably at least 10 carbon atoms per molecule, and moreparticularly from about 20 to about 50 carbon atoms per molecule. Thepreferred acids are referred to herein as high molecular weightpolybasic carboxylic acids and include adipic, pimelic, suberic,azelaic, sebacic, phthalic, etc., aconitic, citric, etc., hemimellitic,trimesic, prehnitic, mellophanic, pyromellitic, mellitic, etc., andhigher molecular polybasic carboxylic acids. It is understood that amixture 'of acids may be employed.

A particular preferred acid comprises a mixed byproduct acid beingmarketed commercially under the trade name of VR-l Acid. This acid isamix-ture of polybasic acids, predominantly dibasic, has an averagemolecular weight by basic titration of about 750, is a liquid at 77 F.,has an acid number of about 150 and iodine of about 36, and containsabout 37 carbon atoms per molecule.

Another particularly preferred acid comprises a mixed acid beingmarketed commercially under the trade name of Empol 1022'. This dimeracid is a dilinoleic acid and is represented by the following generalformula:

- This acidis a viscous liquid, having an apparent molecular weight ofapproximately 600. It has an acid value of 180-192, an iodine value of8095, a saponification value of 185l95, a neutralization equivalent of290-310, a refractive index at 25 C. of 1.4919, a specific gravity at15.5 C./15.5 C. of 0.95, a flash point of 530 F., a fire point of 600F., and a viscosity at 100 C. of 100 centistokes. I

As hereinbefore set forth, dibasic acids containing at least 6 carbonatoms per molecule are preferred. However, it is understood that dibasicacids containing less than 6 carbon atoms also may be employed in somecases and thus include oxalic, malonic, maleic, succinic, glutaric, etc.

In another embodiment, the carboxylic acid used in forming the ester isa reaction product of a terpene and an alpha,beta-unsaturated carboxylicacid or anhydride. Any suitable terpenic compound may be reacted withany suitable alpha,beta-unsaturated polycarboxylic acid or anhydride toform the reaction product for subsequent condensation with theepichlorohydrin-amine condensatiocn product. In one embodiment a terpenehydrocarbon having the formula C I-I is employed, including alphapinene,beta-pinene, dipentane, d-limonene, l-limonene and terpinoline. Theseterpenehydrocarbons have boiling points ranging from about 150". toabout 185 C. In another embodiment the terpene; may. contain three donblebonds in monomeric form, including terpene such as allo-o-cymene,o-cymene, myrcene, etc. Other terpenic compounds includealpha-terpinene, p-cymene, etc.

As hereinbefore set forth, the terpene is reacted with analpha-beta-unsaturated polycarboxylic acid or anhydride thereof. Anyunsaturated polycarboxylic acid having a point of unsaturation betweenthe alpha and beta carbon atoms may be employed. Illustrativeunsaturated dicarboxylic acids include maleic acid, fumaric acid,citraconic acid, mesaconic acid, aconitic acid, itaconic acid, etc.While the dicarboxylic acids are preferred, it is understood thatalpha,beta-unsaturated polycarboxylic acids containing three, four ormore carboxylic acid groups may be employed. Furthermore, it isunderstood that a mixture of alpha,beta-unsaturated polycarboxylic acidsand particularly of alpha,beta-unsaturated dicarboxylic acids may beused.

While the alpha,beta-unsaturated polycarboxylic acid may be employed,advantages appear to be obtained in some cases when using the anhydridesthereof. Illustrative anhydrides include maleic anhydride, citraconicanhydride, aconitic anhydride, itaconic anhydride, etc. It is understoodthat a mixture of anhydrides may be employed and also that the anhydridemay contain substituent-s and particularly hydrocarbon groups attachedthereto.

The reaction of terpene and alpha,beta-unsaturated acid or anhydridegenerally is effected at a temperature of from about to about 300 C.,and preferably of from about to about 200 C. The time of heating willdepend upon the particular reactants and may range from 2 hours to 24hours or more. When desired, a suitable solvent may be utilized.Following the reaction, impurities or unreacted materials may be removedby vacuum distillation or otherwise, to leave a resinous product whichmay be a viscous liquid or a solid.

A terpene-maleic anhydride reaction product is available commerciallyunder the trade name of Petrex Acid. This acid is a stringy,yellow-amber colored mass and is mostly dibasic. It has an acid numberof approximately 530, a molecular weight of approximately 215 and asoftening point of 405 0 C.

In preparing the ester of the condensation product of epihalohydrincompound and amine compound, the aliphatic carboxylic acids generallyare preferred as hereinbefore set forth. However, in some cases, cycliccarboxylic acids may be employed. Aromatic carboxylic acids includebenzoic acid, toluic acid, etc., which acids also may containhydrocarbon and particularly alkyl substituents attached to the ring.Naphthenic carboyxlic acids include cyclopentane carboxylic acid;cyclopentylacetic acid, methylcyclopentyl acid, camphonanic acid,cyclohexane carboxylic acid, methylcyclohexane carboxylic acid,dimethylcyclohexane carboxylic acid, trimethylcyclohexane carboxylicacid, etc.

It is understood that the various acids which may be used in preparingthe ester are not necessarily equivalent and also that mixtures of acidsmay be employed in preparing the esters. In some cases, in place of theacid, the anhydride or certain esters of the acid may be utilized informing the ester with the condensation product of epihalohydrin-amine.These esters may contain up to about 8 carbon atoms in the alcoholportion of the ester but preferably containl or 2 carbon atoms. Thealcohol portion must be volatile under the conditions of theesterification of the epihalohydrin-amine condensation product. In theesterification of the condensation product, transesterification occurs;that is, the smaller alcohol group is volatilized off and replaced bythe epihalohydrinamine condensation product.

The ester of the carboxylic acid and epihalohydrinamine condensationproduct may comprise the partially or completely esterified product. Ashereinbefore set forth, the epihalohydrin-amine condensation product mayand preferably contains a number of recurring units, each of therecurring units having a hydroxyl group. Accordingly, it will be seenthat one, all or any number of the hydroxyl groups may be esterifiedwith the acid. Generally it is preferred to use stoichiometric amountsof these reactants in order to effect substantially completeesterification. One mol equivalent of carboxylic acid will be used pereach equivalent of hydroxyl group in the the epihalohydrin-aminecondensation product.

The ester may be prepared in any suitable manner and, in general, isprepared readily by refluxing the acid and condensation product,preferably with the continuous removal of water formed in the reaction.The refluxing is continued until the theoretical amount of water is collected and thus may range from 1 hour to 48 hours or more at atemperature above about 80 C. Although the esterification may beeffected in the absence of a solvent, which generally will require theuse of vacuum, normally it is preferred to utilize a solvent. The exacttemperature of refluxing will depend upon the particular solventemployed. For example, with benzene as the solvent, the temperature willbe in the order of 80 C., with toluene the temperature will be in theorder of 110 C., and with xylene in the order of 140-145 C. Otherpreferred solvents include cumene, naphtha, decalin, etc. Any suitableamount of the solvent may be employed but preferably should not comprisea large excess because this will tend to lower the reaction temperatureand slow the reaction. Water formed during the reaction may be removedin any suitable manner including, for example, by operating underreduced pressure, by removing an azeotrope of water-solvent, bydistilling the'condensation product at an elevated temperature, etc. Ashereinbefore set forth, a higher temperature and solvent preferably'areutilized in effecting the reaction in order to remove the water as it isbeing formed.

It is understood that the different esters which may be prepared andused in accordance with the present invention are not necessarilyequivalent.

PARTIAL PHOSPHATE SALT OF THE CONDENSATION PRODUCT Another embodiment ofthe invention comprises an HCl salt of a partial phosphate salt of thecondensation product of epihalohydrin compound and amine compound. Ashereinbefore set forth, the condensation product contains a number ofrecurring units, each unit containing a nitrogen atom. In thisembodiment of the invention only a portion of the nitrogen atoms areneutralized with the phosphate, and all or a portion of the remainingnitrogen atoms are neutralized with HCl. Accordingly, this embodiment ofthe invention comprises the mixed HClphosphate salts of the condensationproduct.

In forming the phosphate salt, an alkyl acid phosphate preferably isutilized and may comprise the alkyl acid orthophosphate and/ or thealkyl acid pyrophosphate. In the alkyl acid orthophosphates, themonoalkyl ester, dialkyl ester or a mixture thereof may be employed. Inthe alkyl acid pyrophosphates, the monoalkyl ester, dialkyl ester,trialkyl ester or mixtures thereof may be employed, the dialkyl esterbeing preferred and the alkoxy groups may be attached to the same ordifferent phosphorus atoms. Generally, however, this compound will besymmetrical and, thus, the alkoxy groups will be attached to differentphosphorus atoms.

Preferably at least one of the alkyl groups constituting the estercontains at least 5 and still more preferably at least 8 carbon atoms.Illustrative alkyl acid orthophosphates are set forth below, although itis understood that these are presented as preferred examples and thatother suitable alkyl acid phosphates may be employed. The preferredalkyl acid orthophosphates include monoamyl acid orthophosphate, diamylacid orthophosphate, mixture of monoand diamyl acid orthophosphates,monohexyl acid orthophosphate, dihexyl acid orthophosphate, mixture ofmonoand dihexyl acid orthophosphates,

monoheptyl acid orthophosphate, diheptyl acid orthophosphate, mixture ofmono and diheptyl acid orthophosphates, monooctyl acid orthophosphate,dioctyl acid orthophosphate, mixture of monoand dioctyl acidorthophosphates, monononyl acid orthophosphate, dinonyl acidorthophosphate, mixture of monoand dinonyl acid orthophosphates,monodecyl acid orthophosphate, didecyl acid orthophosphate, mixture ofmonoand didecyl acid orthophosphates, monoundecyl acid orthophosphate,diundecyl acid orthophosphate, mixture of monoand diundecyl acidorthophosphates, monododecyl acid orthophosphate, didodecyl acidorthophosphate, mixture of monoand didodecyl acid orthophosphates,monotridecyl acid orthophosphate, ditridecyl acid orthophosphate,mixture of rnonoand ditridecyl acid orthophosphates, monotetradecyl acidorthophosphate, ditetradecyl acid orthophosphate, mixture of monoandditetradecyl acid orthophosphates, monopentadecyl acid orthophosphate,dipentadecyl acid orthophosphate, mixture of monoand depentadecyl acidorthophosphates, etc.

Preferred alkyl acid pyrophosphates include monooctyl acidpyrophosphate, dioctyl acid pyrophosphate, mixture of monoand dioctylacid pyrophosphates, monononyl acid pyrophosphate, dinonyl acidpyrophosphate, mixture of monoand dinonyl acid pyrophosphates, monodecylacid pyrophosphates, didecyl acid pyrophosphate, mixture of monoanddidecyl acid pyrophosphates, monoundecyl acid pyrophosphate, diundecylacid pyrophosphate, mixture of monoand diundecyl acid pyrophosphates,monododecyl acid pyrophosphate, didodecyl acid pyrophosphate, mixture ofmonoand didodecyl acid pyrophosphates, monotridecyl acid pyrophosphate,ditridecyl acid pyrophosphate, mixture of monoand ditridecyl acidpyrophosphates, monotetradecyl acid pyrophosphate, ditetradecyl acidpyrophosphate, mixture of monoand ditetradecyl acid pyrophosphates,monopentadecyl acid pyrophosphate, dipentadecyl acid pyrophosphate,mixture of monoand dipentadecyl acid pyrophosphates, etc.

Conveniently, alkyl groups containing more than 8 carbon atoms areintroduced through the use of fatty alcohols and thus the alkyl radicalmay be selected from capryl, lauryl, myristyl, palmityl, stearyl, ceryl,etc. Illustrative phosphates in this class include stearyl capryl acidorthophosphate, distearyl acid orthophosphate, dicapryl acidorthophosphate, etc. In other examples, one of the alkyl groups containsless than 8 carbon atoms while the second alkyl group contains more than8 carbon atoms, and such examples are illustrated by ethyl lauryl acidorthophosphate, ethyl stearyl acid orthophosphate, hexyl lauryl acidorthophosphate, hexyl capryl acid orthophosphate, hexyl stearyl acidorthophosphate, etc.

Alkyl acid phosphates including both the ortho and pyrophosphates alsoare manufactured commercially as a mixture of monoand dialkyl acidphosphates and are available at lower costs. In many cases, suchmixtures are suitable for use in preparing the salt and such use,therefore, is preferred for economic reasons.

As hereinbefore set forth, the partial phosphate salt of thecondensation product of epihalohydrin-amine is prepared. Accordingly,the alkyl acid phosphate will be used in a proportion of at least onemol of alkyl acid phosphate per mol of condensation product and willrange up to one mol of phosphate per each mol equivalent less one ofbasic nitrogen in the ester. In general this will comprise from about 2to about 19 mols of phosphate per 1 mol of condensation product. Forexample, as hereinbefore set forth, the preferred condensation productformed by the reaction of one mol of epichlorohydn'n per one mol ofamine compound will contain from about 3 to about 20 and preferably fromabout 5 to about 10 recurring units, each unit containing a basicnitrogen. Accordingly, from about 2 to about 19 mols of phosphate areused per mol of condensation product in order to obtain the desiredpartial phosphate. It is understood that, when a condensation productcontains more than 20 basic nitrogens, a correspondingly larger amountof phosphate may be used.

The partial phosphate of the condensation product may be prepared in anysuitable manner and either before but preferably after the HCl salt isprepared. The phosphate salt is readily prepared by mixing the alkylacid orthophosphate and the condensation product, preferably the HClsalt of the condensation product, at ambient temperature, with vigorousstirring, although slightly elevated temperatures which generally willnot exceed '200 F. may be employed, when desired. Excessive temperaturesmust not be used in order to avoid decomposition reactions. In fact, thereaction is slightly exothermic and in some cases it may be desirable tocool the reaction vessel. The reaction may be effected in the presenceor absence of a solvent. When employed, the sol- -vent may be usedeither in forming a more fluid mixture of the reactants before mixingand/or during the mixing thereof. Any suitable solvent may be employedand preferably is an aromatic hydrocarbon including benzene, toluene,xylene, ethylbenzene, cumene, etc., or mixtures thereof. In other casesthe solvent may be selected from alcohols, ethers, ketones, etc. In manycases it is desired to market the final product as a solution in asuitable solvent and conveniently the same solvent is used during thepreparation of the phosphate and/or HCl salts. i

PARTIAL PHOSPHATE SALT OF THE ESTER OF THE CONDENSATION PRODUCT In stillanother embodiment, the additive of the present invention comprises anHCl salt of the partial phosphate salt of the ester of the condensationproduct. Accordingly, the additive comprises the mixed HCl-phosphatesalt of the ester. The phosphate salt of the ester is prepared insubstantially the same manner as heretofore described in detail for thepreparation of the partial phosphate salt ofthe condensation product.Instead of thecondensation product, an ester thereof prepared in themanner as hereinbefore set forth in the description of the preparationof the ester, is reacted with the alkyl acid phosphate. Here again,preferably the HCl salt is formed first and then the phosphate salt ofthe ester is prepared. Because the preparation of the ester and thepreparation of the partial phosphate salt have been described in detailhereinbefore, it is unnecessary to repeat the details to describe. thepreparation of the partial phosphate salt of the ester. A specificpreparation will be described in the appended examples.

HCl SALT As hereinbefore set fonth,'the novel additive of the presentinvention comprises an HCl salt of the condensation product of anepihalohydrin compound with an amine, a carboxylic acid ester thereof orpartial phosphate salt of the condensation product or ester. Preferablyonly a portion of the amino nitrogen in said condensation product orester are neutralized. Of necessity, only a portion of .the aminonitrogens of the partial phosphate salt will be neutralized. It isrecognized that the HCl'salt will be less soluble in hydrocarbon oilthan the condensation product, ester or partial phosphate salt and,therefore, it is important that the extent of neutralization with HCl bebelow that exceeding solubility of the hydrocarbon oil. At least 0.2% ofthe amino nitrogens will be neutralized with HCl, and the upper limit ofneutralization with HCl will be that at which solubility of the additivein the hydrocarbon oil is exceeded. The solubility is determined by theconcentration of additive to be incorporated in the oil. In general itis preferred that from about 1% to about 20% ofthe amino nitrogen isneutralized with HCl.

gen compounds, oxygen compounds, metals, etc.

Neutralization with H01 is effected in any suitable manner and ingeneral is readily accomplished by heating, with stirring, a mixture ofthe condensation product, ester or partial phosphate salt and HCl. TheHCl may be utilized as a gas in a closed system. However, it preferablyis utilized as a solution in a suitable solvent in cluding alcohol,water, etc. The lower alcohols are preferred solvents and includemethanol, ethanol, propanol, and butanol. In general the reaction iseffected at ambient or elevated temperature, which may range from about50 to about C. and, as stated before, with stirring. Higher temperaturesmay be used in some cases, but generally offer no advantages. When asolvent is employed, it may be removed by distillation under vacuum orin any other suitable manner, although in some cases it may be desirableto market the additive as a solution in the solvent. When water is usedas the solvent, the water preferably is removed by azeotropicdistillation.

The HCl salt recovered in the above manner may be utilized as such orprepared as a solution in a suitable solvent. Aromatic hydrocarbons areparticularly preferred solvents and include benzene, toluene, xylene,ethylbenzene, cumene, etc. It is understood that other suitable organiccompounds and particularly paraflinic hydrocarbons may be used assolvents.

The additive prepared in the above manner is incorporated in ahydrocarbon oil in an amount of from about 1 to about 1000 parts permillion by Weight of the hydrocarbon oil and preferably in aconcentration of from about 5 to about 100 parts per million, althoughhigher concentrations up to 1% by weight may be used in some cases andthus may range from about 0.0005% to about 1% by weight.

As hereinbefore set forth, the salt of the present in vention is used toprevent deposit formation in heat exchangers. In such heat exchange onefiuid is passed through tubes or coils disposed in a shell and the otherfluid is passed through the shell. The oil heated in this manner then ispassed for further treatment, While the oil cooled in this manner ispassed to separation or further conversion. It is understood that thehydrocarbon oil may comprise gasoline, naphtha, kerosene, gas oil,burner oil, diesel oil, fuel oil, residual oil, etc.

An example of a process in which-the charge is passed in heat exchangewith hot effluent products is a hydrotreating process in which oil issubjected to hydrogen treating in the presence of a catalyst comprisingaluminamolybdenum oxide-cobalt oxide or alumina-molybdenumsulfide-cobalt sulfide. The oil may comprise gasoline, kerosene, gas oilor mixtures thereof and is treated to remove impurities including sulfurcompounds, nitro- The treating is effected at. a temperature within therange of from about 500 to about 800 F. or more at hydrogen pressures offrom about 100 to about 1000 pounds per square inch or more. The oilcharged to the process generally is introduced at a temperature of fromambient to 200 F. and is passed in heat exchange with products withdrawnfrom the reactor at a temperature of from about 500 to about 800 F.During this heat exchange the charge is heated to a temperature of fromabout 300 to about 600 F. and then may be heated further in a furnace orotherwise to the temperature desired for effecting the treating. At thesame time the hot reactor efiluent products are cooled to a temperatureof from about 300 to about 600 F. and below that at which they arewithdrawn from the reactor. Generally the partly cooled reactor effiuentproducts are cooled further by heat exchange with water or otherwise andthen are passed into a separator, wherefrom gases and liquids are eachseparately withdrawn. Another illustrative example of a process in whichthe charge is passed in heat exchange with reactor eflluent products isa reforming process in which gasoline is contacted with hydrogen in 11the presence of a platinum-containing catalyst at a temperature of fromabout 700 to about 1000 F.

An example in which oil is subjected to fractionation and the charge ispassed in heat exchange with the hot efiluent products is in a crudecolumn. In this column, crude oil is subjected to distillation at atemperature of from about 600 to about 700 F. in order to remove lightercomponents as overhead and/or side streams. In some cases the chargefirst is passed in heat exchange with the overhead and/or side streamsfrom this column and then is passed in heat exchange with the hotterproducts withdrawn from the bottom of the crude column. In this way thecharge is progressively heated and the hotter products are cooled.

Normally the charge to the treating or conversion process containscomponents which form deposits in the heat exchangers and, accordingly,the salt of the present invention is incorporated in the charge prior toentering the heat exchanger. In most cases the charge after heatexchange is subjected to fractionation to separate a particular streamfor subjecting to further treating or conversion in the presence of acatalyst. Generally this stream comprises the light or intermediatecomponents of the charge, and the heavier components of the charge areremoved from the process. In most cases the salt will be retained in thebottoms product and therefore will not contact the catalyst used in thesubsequent treating or conversion steps. However, the salt in the smallconcentrations used will not adversely affect most catalysts, andtherefore would be of concern only with processes using catalysts ofextreme sensitivity. As stated above, even with such catalysts, theprefractionation will serve to retain the salt in the heavier productsand the salt therefore will not contact the catalyst.

Another example in which hydrocarbon oil is passed in heat exchange isin the case of jet fuel, wherein the jet fuel is passed in heat exchangewith hot lubricating oil. Temperatures as high as 500 F. or more areencountered for at least short periods of time, with the result thatdeposit formation occurs and either interferes with efficient heattransfer or, in extreme cases, plugs the heat exchanger.

As hereinbefore set forth, the additive of the present invention alsomay be used to improve the storage stability and other properties ofhydrocarbon oil. These hydrocarbon oils include gasoline, naphtha,kerosene, gas oil, burner oil, diesel oil, fuel oil, lubricating oil,residual oil, etc.

While the present invention is particularly applicable to the treatmentof hydrocarbon fluids, it is understood that it may be employed withother organic fluids which cause deposit formation in heat exchangers asin storage. Such other organic fluids include alcohols, aldehydes,ketones, detergents, pharmaceuticals, organic intermediates, etc.

It is understood that the salt of the present invention may be usedalong with other additives including, for example, antioxidant, metaldeactivator, corrosion inhibitor, detergent, dye, etc. The specificadditive to be used will depend upon the particular hydrocarbon oilbeing treated.

The following examples are introduced to illustrate further the noveltyand utility of the present invention but not with the intention ofunduly limiting the same.

Example I A number of different HCl salts of the condensation product ofepichlorohydrin and tallow amine were prepared. The condensation productwas prepared by the reaction of equal mol proportions of hydrogenatedtallow amine (Armeen HTD) and epichlorohydrin. It will be noted that thetallow amine is a mixture of primary alkyl amines predominating in 16 to18 carbon atoms per alkyl group. The reaction was eifected by firstforming a solution of 2 mols of epichlorohydrin in 600 cc. of a solventmixture comprising 400 cc. of xylene and 200 cc. of 2-propanol. Aseparate solution of 2 mols of Armeen HTD was prepared in an equalvolume of xylene. One mol of the latter solution was added gradually tothe epichlorohydrin solution, with stirring and heating at 55-60 C. 5for a period of 2.5 hours. Then another mol of Armeen HT D was addedgradually to the reaction mixture, stirred and reacted at 80 C. for 2.5hours. One mol of sodium hydroxide then was added with stirring andheating at 85-90 C. for 3.5 hours, after which another mol of sodiumhydroxide was added and the mixture stirred and reacted at 8590 C. forone hour; Following completion of the reaction, the mixture was cooled,filtered, and the filtrate then was distilled to remove the alcohol. Thecondensation product was recovered as a 50% by weight solution of activeingredient in xylene.

The HCl salts of the condensation product formed in the above mannerwere prepared by reacting a specified concentration. of H01 in the formof 0.0951 N alcoholic HCl with different samples of the condensationproduct. All of these preparations were made by mixing the reactants asstated above at room temperature, with stirring, then heating on a waterbath to a temperature of about 95 C. for about 1 hour, following whichthe rest of the alcohol was removed by distillation under water pumpvacuum. Additional xylene was then added to each preparation to form afinal solution of 50% by weight active ingredient.

The specific details of preparation and certain analytical data arereported in the following table:

Gms. of cc. of Percent of condensaalcoholic amino Additive Number tionHO] nitrogen product neutralized with H Cl 7 As hereinbefore set forth,the above salts were recovered as solutions in xylene of by weightactive ininvention are particularly desirable for use to prevent heatexchanger deposits. The difierent additives prepared as described inExample I were evaluated in the CPR. fuel coker thermal stability test.In this test, the oil heated to the specified temperature is passedthrough the annular space surrounding a heated inside tube of 17" lengthand /2" diameter positioned within an outside tube of inside diameter.The inside tube is heated by means of a heating coil positioned thereinto a temperature of either 300 or 400 F. depending upon the particularfuel being evaluated. The test is conducted for 300 minutes, at apressure of 160 pounds per square inch, and a flow rate of 6 pounds offuel per hour. Following the run the equipment is dismantled, 13" orless of the inner tube is marked off in 1" increments, and the depositson the heated inner tube are rated by visual comparison with standardmetal coupons. In general the rating is substantially as follows:

clean and bright metal dulled but not discolored light yellowdiscoloration yellow to tan discoloration anything darker or heavierthan 3 76 The ratings of the individual 1" increments are added togetherto give a final tube rating. Military specificaticns for jet fuelsrequire that none of the 1" increments rate poorer than 3.

' The fuel used in these evaluation-s is a commercial heavy catalyticnaphtha and was tested at a temperatude of 400 F. A control sample (notcontaining an additive) of the naphtha gave a tube rating of 26 whenevaluated in the above manner. The results of evaluating the differentsamples of the naphtha containing the additives described in Example Iare reported in the following table. The additive was incorporated in aconcentration of 0. .005 by weight of active ingredient.

From the data in the above table it will be noted that the additives ofthe present invention all served to reduce the tube rating to aboutone-half of that obtained in the absence of the additive. Ashereinbefore set forth, this serves to reduce deposit formation in heatexchangers.

' Example III l The additive of this example is an HCl salt of an esterof the condensation product prepared in the manner described in ExampleI. The ester is the VR-l acid ester. As hereinbefore set forth, VR-lacid is a mixture of polybasic acids, predominantly dib asic, containingabout 37 carbon atoms per molecule. The ester was prepared by mixing63.8 grams of the condensation product prepared as described above, 34.3grams of VR-1 acid and 100 cc. ofxylene. The mixture was heated, withstirring, to atemperature of about 141 C. and refluxed for about 9hours. The mixture was cooled and distilled under vacuum at about 155 C.to remove the xylene. The product was recovered as a viscous dark liquidand was blended with additional xylene to prepare a solution of 50% byweight active ingredient. grams of the ester solution prepared in theabove manner were mixed with 1.6 cc. of 0.0951 N alcoholic HCl andheated, with stirring, to a temperature of about 98 C. for about 1 hour,after which the rest of the alcohol was removed by distilling underWater pump vacuum. Sufficient xylene was added to form a final solutionof 50% by weight active ingredient. This product was a dark brown,opaque, free-fiowing liquid, having an index of refraction (11 of1.4867. The salt prepared in the above manner was evaluated according tothe 'C.F.R. fuel coker thermal stability test described in Example II.The control sample (not containing an additive) of the oil used in thisexample had a'tube' rating of 20. 'Another sample of the oil containing0.005% by'weight of active ingredient of the salt prepared as describedabove, when evaluated in this manner, had a tube rating of 12. Hereagain it will be noted that the additiveof the present invention wasefiective inreducing deposit formation.

" Example IV 7 As .hereinbefore set forth, another embodiment of theinventioncornprises mixed HCl-phosphate salts of the condensation prduct of epihalohydrin with amine. The

phosphate salt is the mixed monoand ditridecyl acid orthophospha-te saltof the condensation product prepared as described in Example I. In thispreparation the HCl salt was prepared first and then the phosphate saltwas prepared.

100 grams of the 50% active ingredient solution of the condensationproduct prepared in the manner described in Example I and 156 cc. of0.0951 N HCl solution in isopropanol were commingled at room temperatureand reacted with stirring for 15 minutes. 49.3 grams of mixed monoanddi-tridecyl acid orthophosphate were commingled therewith and themixture heated, with stirring, to 50 C. for 45 minutes. The mixture thenwas distilled under water pump vacuum to remove the rest of the alcohol.Sufficient xylene then was commingled with the product to produce a 50%solution active ingredient. This solution was recovered as an amber,free-flowing liquid, having an index of refraction (n of 1.4787.

The mixed HCl-phosphate salt prepared in the above manner was evaluatedaccording to the CPR. fuel coker thermal stability test described inExample II. The oil used in this example is a commercial J.P.4 jet fueland the test was conducted at a temperature of 300 F. A control sample(not containing an additive) of the jet fuel, when evaluated in theabove manner, had a tube rating of 34. In contrast, another sample ofthe jet fuel containing 0.0025 by weight of the mixed HCl-phosphate saltsolution (0.00125% by. Weight of active ingredient) described above,when evaluated in the above manner, had a tube rating of zero. It isapparent that the additive of the present invention was very elfectivein reducing deposit formation.

Example V As hereinbefore set forth, the additive of the presentinvention also is effective to prevent sediment formation in hydrocarbonoil. The sediment formation will cause plugging of filters, strainers,burner tips, injectors, etc., and the efiicacy of the additive isevaluated in a method referred to as the Erdco Test. In this method,heated oil is passed through a filter, land the time required to developa differential pressure across the filter of 25 in. Hg is determined. Itis apparent that the longer the time, the more effective is theadditive. However, with a very effective additive, the time to reach adilferential pressure across the filter of 25 in. Hg is lengthenedbeyond reasonable limits and the test is stopped after about 300 minutesand the differential pressure at that time is reported. The oil used inthis example is the J.P.-4 jet fuel described in Example IV. In thistest the preheater was run at 300 F. and the filter at 400F.

When evaluated in the above manner a control sample (not containing anadditive) of the jet fuel developed a differential pressure across thefilter of 25 in. Hg in minutes. On the other hand, another sample ofthis jet fuel containing 0.0025 by weight of the mixed HCl-phosphatesalt solution (0.00125 by Weight active ingredient) described in ExampleIV, developed a difierential pressure of only 0.05 in. Hg after 300minutes.

Example VI The mixed HCl-phosphate salt prepared as described in ExampleIV also was evaluated in the Erdco test in a commercial J.P.-6 fuel.This test was-conducted using a preheater temperature of 400 F. and afilter temperature of 500 F.

A control sample (not containing an additive) of the J.P.6 jet fuel,when evaluated in the Erdco test as described above, developed adifferential pressure of 25 in. Hg in 51 minutes. On the other hand,another sample of the jet fuel containing 0.0025 by weight of the 50%solution (0.00125 active ingredient) of the mixed HCl-phosphate saltprepared as described in Example IV, developed a zero in. Hg pressureafter 300 minutes.

At the same time, the preheater tube rating of the mixed HCl-phosphatesalt described above was evaluated. A control sample (not containing anadditive) of the J.P.6 fuel had a tube rating of 15. The sample of theJ.P.6 fuel containing the mixed HCl-phosphate salt described above had atube rating of only 6. From the above data it will be seen that theadditive was very effective in preventing filter plugging and tubedeposits.

Example VII The additive of this example is the mixed HCl-phosphate saltof an ester of the condensation product of epichlorohydrin and tallowamine. The condensation product was prepared substantially in the samemanner as described in Example I. The ester was prepared by refluxing100 grams of the 50% active solution of the condensation product, 42grams of oleic acid and 50 cc. of xylene. The refluxing was effected atabout 150 C. for 15 hours. An 0.1 N solution of HCl-ethanol is mixedwith the ester prepared in the above manner and the mixture is heated,with stirring, at 85 C. for 1 hour. The HCl is used in a concentrationto neutralize of the basic amino nitrogen. Mixed monoand diisooctyl acidorthophosphate is added to the mixture and heated, with stirring, at 50C. for 40 minutes. Sufficient xylene then is added to produce a finalsolution of 50% by weight active ingredient.

The mixed HCl-phosphate salt of the ester prepared in the above manneris incorporated in a straight run oil having a boiling range of fromabout 300 to about 700 R, which oil is passed in heat exchange with hotreactor efiluent products. The thus preheated charge then is heated in afurnace to a temperature of 600 F. and passed in contact withalumina-molybdenum oxidecobalt oxide catalyst to remove sulfur, nitrogenand other impurities from the oil. The reactor efiluent products arepassed in heat exchange with the charge as described above and then aresent to a separator for the removal of hydrogen and hydrocarbon gases,after which the oil is sent to a fractionating zone to separate anaphtha having an end boiling point of 400 F. and a heavier oil having aboiling range of from about 400 to about 700 F.

I claim as my invention:

1. Hydrocarbon oil containing from about 0.0005% to about 1% by Weightof an oil soluble HCl salt of the condensation product, formed at atemperature of from about 20 C. to about 150 C., of equimolar amounts ofepichlorohydrin and an alkyl amine having from about 12 to about 40carbon atoms per molecule, from about 1% to about 20% of the aminonitrogen in said condensation product being neutralized with HCl.

2. Hydrocarbon oil containing from about 0.0005% to about 1% by weightof an oil soluble HCl salt of the condensation product, formed at atemperature of from about 20 C. to about 150 C., of equimolar amounts ofepichlorohydrin and tallow amine, from about 1% to about 20% of theamino nitrogen in said condensation product being neutralized with HCl.

3. Hydrocarbon oil containing from about 0.0005 to about 1% by weight ofan oil soluble HCl salt of an ester of carboxylic acid containing fromabout 6 to about 50 carbon atoms per molecule and the condensationproduct, formed at a temperature of from about 20 C. to about 150 C., ofequimolar amounts of epichlorohydrin and an alkyl amine of from about 12to about 40 carbon atoms per molecule, from about 1% to about 20% of theamino nitrogen in said condensation product being neutralized with HCland the amount of carboxylic acid being sufficient to esterify from oneto all of the hydroxyl groups in the condensation product.

4. Hydrocarbon oil containing from about 0.0005% to about 1% by weightof an oil soluble mixed HCl-alkyl acid phosphate salt of thecondensation product, formed at a temperature of from about 20 C.v toabout 150 C.,

of equimolar amounts of epichlorohydrin and an alkyl amine of from.about 12 to about 40 carbon atoms per molecule, from about 1% to about20% of the amino nitrogen in said condensation product being neutralizedwith HCl and the amount of alkyl acid phosphate being at least one molof phosphate per mol of the condensation product.

5. Hydrocarbon oil containing from about 0.0005 to about 1% by weight ofan oil soluble HCl salt of the condensation product, formed at atemperature of from about 20 C. to about C., of from 1 to 2 mols of analiphatic amine containing from about 12 to about 40 carbon atoms permolecule with from 1 to 2 mols of an epihalohydrin compound selectedfrom the group consisting of epichlorohydrin, 1,2-epi-4-chlorobutane,2,3-epi- 4-chlorobutane, 1,2-epi-5-chloropentane,2,3-epi-5-ch1oropentane and corresponding bromo and iodo compounds, fromabout 1% to about 20% of the amino nitrogen in said condensation productbeing neutralized with HCl.

6. Hydrocarbon oil containing from about 0.0005% to about 1% by weightof an oil soluble HCl salt of an ester of stoichiometric amounts of analiphatic carboxylic acid of from about 6 to about 50 carbon atoms permolecule and the condensation product, formed at a temperature of fromabout 20 C. to about 150 C., of from 1 to 2 mols of an alkyl aminecontaining from about 12 to about 40 carbon atoms per molecule with from1 to 2 mols of an epihalohydrin compound selected from the groupconsisting of epichlorohydrin, 1,2-epi-4-chlorobutane,2,3-epi-4-chlorobutane, 1,2-epi-5-chloropentane, 2,3-epi-5-chloropentaneand corresponding bromo and iodo compounds, from about 1% to about 20%of the amino nitrogen in said condensation product being neutralizedwith HCl.

7. Hydrocarbon oil containing from about 0.0005 to about 1% by weight ofan oil soluble mixed HCl-alkyl acid phosphate salt of the condensationproduct, formed at a temperature of from about 20 C. to about 150 C., offrom 1 to 2 mols of an alkyl amine containing from about 12 to about 40carbon atoms per molecule with from 1 to 2 mols of an epihalohydrincompound selected from the group consisting of epichlorohydrin,1,2-epi-4- chlorobutane, 2,3-epi-4-chlorobutane,1,2-epi-5-chloropentane, 2,3-epi-5-chloropentane and corresponding bromoand iodo compounds, from about 1% to about 20% of the amino nitrogen insaid condensation product being neutralized with HCl and the amount ofalkyl acid phosphate being at least one mol of phosphate per mol of thecondensation product.

References Cited in the file of this patent UNITED STATES PATENTS1,954,133 Jacob Apr. 10, 1934 2,089,212 Kritchevsky Aug. 10, 19372,130,947 Carothers Sept. 20, 1938 2,143,388 Schlack Jan. 10, 19392,214,352 Schoeller et al. Sept. 10, 1940 2,348,842 Paul May 16, 19442,454,547 Bock et al. Nov. 23, 1948 2,475,410 Smith et al. July 5, 19492,627,521 Coover Feb. 3, 1953 2,660,563 Banes et al Nov. 24, 19532,695,222 Chenicek et a1 Nov. 23, 1954 2,759,021 Gaar et al Aug. 14,1956 2,763,614 Cantrell et al. Sept. 18, 1956 2,854,323 Shen et al.Sept. 30, 1958 2,863,742 Cantrell et al. Dec. 9, 1958 2,908,640Dougherty Oct. 13, 1959

1. HYDROCARBON OIL CONTAINING OIL FROM ABOUT 0.0005% TO ABOUT 1% BYWEIGHT OF AN OIL SOLUBLE HCI SALT OF THE CONDENSATION PRODUCT, FORMED ATA TEMPERATURE OF FROM ABOUT 20*C. TO ABOUT 150*C., OF EQULIMOLAR AMOUNTSOF EPICHLOROHYDRIN AN AN ALKY AMINE HAVING FROM ABOUT 12 TO ABOUT 40CARBON ATOMS PER MOLECULE, FROM ABOUT 1% TO ABOUT 20% OF THE AMINONITROGEN IN SAID CONDENSATION PRODUCT BEING NEUTRALIZED WITH HCI.